Oil Thinning Compositions And Retrieval Methods

ABSTRACT

The present invention relates to compositions of plant oil-based biodegradable crude oil thinning fluids having a performance especially suitable to reducing crude oil viscosity in extraction and retrieval operations.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U. S. C. § 119 fromProvisional Application Ser. No. 61/543,185, filed Oct. 4, 2011, thedisclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to compositions of plant oil-basedbiodegradable crude oil thinning fluids having a performance especiallysuitable to reducing crude oil viscosity in extraction and retrievaloperations.

BACKGROUND OF THE INVENTION

With ever increasing environmental pressures being placed on the oilindustry it has become necessary to develop and employ products andmethods of well treatment which can perform in a timely fashion, be costeffective and conform to the stricter controls now in place.

It is known in the art that oil fields can become extremely viscous dueto a heavy concentration of paraffin, asphaltene, or a combination ofboth and other organics in the formation. Paraffin plugs stop oilrecovery completely until they are cleared. Indeed, these deposits canresult in reduced oil production, fouling of flow lines and down holepiping, under deposit corrosions, reductions in gas production, andincreased pumping costs due to pumping a high viscosity fluid. Each ofthese conditions individually can result in lost revenue. Thecombination of two or more of these conditions will lead to asignificant revenue loss to the well owner, as well as additional incomespent due to clean up of oil spills caused by under deposit corrosion orother flow restrictions. Moreover, the differing oxygen concentrations(and other corrosive compounds which may be present and intensify thecorrosiveness of the oil) in bulk oil with respect to the oxygen levelsextant beneath the deposit result in localized, rapid corrosion of thepiping and eventual oil leaks. What is needed is a environmentallyfriendly, recyleable composition and methods for reducing the viscosityof crude oils in the field to facilitate extraction.

SUMMARY OF THE INVENTION

The present invention relates to compositions of plant oil-basedbiodegradable crude oil thinning fluids, having a performance especiallysuitable to reducing crude oil viscosity in extraction and retrievaloperations.

In one embodiment, the present invention comprises formulations andmethods to enhance recovery from an oil well field. In one embodiment,the applicant's method supplies a mixture of terpenoid compounds derivedfrom d-limonene, soy methyl esters, and non-toxic glycol ether estersreacted in a specific sequence with inorganic catalyst to yield amixture the effectively reduces the viscosity of crude oil and oilsands. In one embodiment, the method continues the extraction ofmaterials from the oil well or oil sands wth the mixture of—limonene,soy methyl esters, and non-toxic glycol ether esters into the oil wellor sands reducting the material's viscosity. In one embodiment, themethod recirculates the oil well, and then returns the oil well toservice enabling extraction of additional oil with reduced effort.

In one embodiment, the invention relates to a method to recover oil froman oil well, comprising the steps of: a) providing a formulationcomprising: one or more terpenoid compounds, soy methyl esters, andglycol ether esters; b) introducing a said formulation into said oilwell; and c) recovering a mixture from said oil well, said mixturecomprising at least a portion of said formulation and oil from said oilwell. In one embodiment, the invention relates to a method to recoveroil from an oil well, comprising the steps of: a) providing aformulation comprising: one or more terpenoid compounds, soy methylesters, and glycol ether esters; b) introducing a first portion of saidformulation into said oil well; and c) recovering a mixture from saidoil well, said mixture comprising at least a portion of said formulationand oil from said oil well. In one embodiment, said oil well is notproducing oil using standard extraction techniques. In one embodiment,said oil well is producing oil using standard extraction techniques. Inone embodiment, the method further comprises, prior to said introducingof step b), the step of discontinuing extraction of materials from saidoil well by said standard extraction techniques. In one embodiment, themethod further comprises, after said recovering of step c), the step ofrecirculating said oil well. In one embodiment, the method furthercomprises, after said recirculating, the step of returning said oil wellto service and extracting oil by standard extraction techniques. In oneembodiment, said formulation comprises approximately 30-35 or even 30-45weight percent of said one or more terpenoid compounds, approximately30-35 or even 30-45 weight percent of said methyl esters, and thebalance of weight percent of said glycol ether esters. In oneembodiment, said one or more terpenoid compounds comprise one or more ofpinene, menthene, menthane, and limonene. In one embodiment, said one ormore terpenoid compounds comprises at least D-limonene. In oneembodiment, the present invention contemplates making monoterpenes fromsoybean oil and their derivatives. In one embodiment, the method furthercomprises after said recirculating step the steps of: introducing asecond portion of said formulation into said oil well. In oneembodiment, said second portion is introduced under pressure (e.g.greater than ambient atmospheric pressure). In another embodiments,different pressures are used over time (e.g. 24 to 72 hours). In oneembodiment, said first pressure is between about 200 psi and about 1000psi, and wherein said second pressure is between about 400 psi and about1200 psi, and wherein said third pressure is between about 600 psi andabout 1400 psi.

In one embodiment, the invention relates to a formulation comprising oneor more terpenoid compounds, soy methyl esters, and glycol ether esters.In one embodiment, the formulation comprises approximately 30-35 weightpercent of said one or more terpenoid compounds, approximately 30-35weight percent of said methyl esters, and about 30 weight percent ofsaid glycol ether esters. In one embodiment, the formulation issubtantially non-toxic.

In one embodiment, the invention relates to a method for producing aformulation to dispose in an oil well to enhance recovery therefrom,comprising: a. providing i) a solution of one or more terpenoidcompounds, ii) soy methyl esters, iii) glycol ether esters, iv) a firstinorganic catalyst, v) a second inorganic catalyst, and vi) a reactor;b. placing said solution of one or more terpenoid compounds in saidreactor, c. suspending said first inorganic catalyst in said solution insaid reactor; d. adding said soy methyl esters to the reactor to createa first reaction mixture; e. agitating said first reaction mixture; andf. adding said glycol ether esters to said reaction mixture in thepresence of said second inorganic catalyst to create a second reactionmixture; and g. agitating said second reaction mixture so as to producea formulation for recovering oil. In one embodiment, said reactor is astainless steel reactor. In one embodiment, said reactor is a glassreactor with an added source of steel. In one embodiment, said reactoris a plastic reactor with an added source of steel. In one embodiment,agitating comprises stirring the mixture for at least 30 minutes at1700-3500 rpm. In one embodiment, said reactor is grounded. In oneembodiment, agitating comprises stirring the mixture until the solutionis clear. In one embodiment, the invention is the composition producedaccording to the method above. In one embodiment, the composition can beused to reduce the viscosity of oil in pipes. In one embodiment, thecomposition can be used to increase the extraction of oil from oilsands. In one embodiment, the composition is subtantially non-toxic.

In one embodiment the invention relates to a method to enhance recoveryfrom an oil well, comprising the steps of: supplying a mixture ofcompounds comprising: a mixture of one or more terpenoid compounds, soymethyl esters, and glycol ether esters; discontinuing the extraction ofmaterials from said oil well; disposing said mixture of compounds intosaid oil well; recirculating said oil well; returning said oil well toservice. In one embodiment, said supplying a mixture of compoundsfurther comprises supplying a mixture comprising about 30-35 or even30-45 weight percent of said a mixture of one or more terpenoidcompounds, about 30-35 or even 30-45 weight percent of said methylesters, and the balance of weight percent of said glycol ether esters.In one embodiment, said one or more terpenoid compounds comprise one ormore of pinene, menthene, menthane, and limonene. In one embodiment,said mixture of one or more terpenoid compounds comprises at leastD-limonene. In one embodiment, the method further comprising after saidrecirculating step the steps of: injecting said mixture of compoundsinto said oil well using a first pressure, wherein said first pressureis greater than ambient atmospheric pressure; wherein said secondpressure is greater than ambient atmospheric pressure; maintaining athird pressure in said well for 24 to 72 hours, wherein said thirdpressure is greater than ambient atmospheric pressure. In oneembodiment, said first pressure is between about 200 psi and about 1000psi, and wherein said second pressure is between about 400 psi and about1200 psi, and wherein said third pressure is between about 600 psi andabout 1400 psi.

In another embodiment, the invention relates to a formulation to disposein an oil well to enhance recovery therefrom, comprising a mixture ofmixture of compounds comprising a mixture of one or more terpenoidcompounds, soy methyl esters, and glycol ether esters. In oneembodiment, the mixture of compounds further comprises about 30-35 oreven 30-45 weight percent of said a mixture of one or more terpenoidcompounds, about 30-35 or even 30-45 weight percent of said methylesters, and the balance of weight percent of said glycol ether esters.

In another embodiment, the invention relates to a method for producing aformulation to dispose in an oil well to enhance recovery therefrom,comprising: a) one or more terpenoid compounds, soy methyl esters,glycol ether esters, a first inorganic catalyst, a second inorganiccatalyst, b) 30-35% weight by weight of the terpenoid compoundd-limonene is placed in a reactor and said first inorganic catalyst issuspended in the solution of d-limonene; c) addition of 30-35% soymethyl esters to the reactor and subsequent agitation of the resultingmixture; and d) slow addition of glycol ether esters by weight to makeup the balance of the mixture in the presence of said second inorganiccatalyst and subsequent agitation of the solution. In one embodiment,said reactor is a stainless steel reactor. In one embodiment, saidreactor is a glass reactor with an added source of steel. In oneembodiment, said reactor is a plastic reactor with an added source ofsteel. In one embodiment, said first inorganic catalyst is a copper/ironcatalyst. In one embodiment, agitation comprises stirring the mixturefor at least 30 minutes at 1700-3500 rpm. In one embodiment, saidreactor is grounded. In one embodiment, step d further comprisesstirring the mixture until the solution is clear. In one embodiment,said second inorganic catalyst is a copper/iron catalyst. In oneembodiment, the invention is the composition produced according tomethod described above. In all instances, the reactions are endothermic.

In one embodiment, the invention relates to crude oil thinningformulations including, but not limited to:

1. In one embodiment, a family of formulations which use the solventdiscoveries and other organic compounds to increase the recovery orcrude oil form the geologic formation, the reservoir, and the oill tarsands. In one embodiment, this includes the chemistry and methods of oilrecovery in the tar sands and oil rock/shale. We have experimentallyincreased the yield of oil by up to 10 times, and maintained that flowfor 6-12 weeks.

2. In one embodiment, viscosity reducers which work outside the oilmolecule which allows for at least 80% recovery, more preferably atleast 90% recovery, and most preferably up to 100% recovery of ourformulations with either mechanical or simple low temperaturedistillation techniques. In one embodiment, charged particle theoryusing the outermost ring of electrons to separate the oil molecules,reducing the cohesive properties of oil.

3. In one embodiment, pipeline thinning agents which reduce theviscosity and the operating temperature requirements, and eliminate theneed for corrosion preventatives, synthetic oil additions andsub-sequent separation, and readily allow for the addition ofcondensates, which can be separated and recovered though either physicalmechanical separation or distillation.

4. In one embodiment, paraffin plug treatment agents to resume orrestore flow.

In one embodiment, the invention relates to a method to improve oil flowfrom an oil pipe, comprising the steps of: a) providing a formulationcomprising: one or more terpenoid compounds, soy methyl esters, andglycol ether esters; b) introducing a first portion of said formulationinto said oil pipe; and c) recovering a mixture from said oil pipe, saidmixture comprising at least a portion of said formulation and oil fromsaid oil pipe. In one embodiment, the mixture can be added to oil fieldpipes in order to increase flow. In one embodiment, the mixture can beadded to oil field pipes in order to clear a blockage. In oneembodiment, the blockage comprises a paraffin plug. In one embodiment,the mixture comprises a paraffin plug treatment. In one embodiment, thepipes are buried. In one embodiment, the pipes are remotely located. Inone embodiment, the pipes are exposed to extreme temperatures (e.g. −60°C. to +40° C.). In one embodiment, the pipes are exposed to very lowtemperatures. In one embodiment, the mixture is added to said oil pipeto enable the recovery of otherwise uncapturable oil.

In one embodiment, the invention relates to a method of separating theoil from the mixture. In one embodiment, a large portion of the mixtureis substantially recovered. In one embodiment, the recovery of themixture is at least 80%, and more preferably at least 90%. In oneembodiment, the recovered mixture is substantially nontoxic. In oneembodiment, the recovered mixture is nontoxic. In one embodiment, therecovered mixture is recovered though a combination of physicalmechanical separation and distillation. In one embodiment, the recoveredmixture is recovered though physical mechanical separation. In oneembodiment, the recovered mixture is recovered though distillation. Inone embodiment, the recovered mixture may reused in the same fashion asthe original mixture with little or no reduction in performance.

In one embodiment, the invention relates to a method to recover oil froman oil sands, comprising the steps of: a) providing a formulationcomprising: one or more terpenoid compounds, soy methyl esters, andglycol ether esters; b) introducing a first portion of said formulationinto said oil sands; and c) recovering a mixture from said oil sands,said mixture comprising at least a portion of said formulation and oilfrom said oil sands. In one embodiment, said oil sands is not producingoil using standard extraction techniques. In one embodiment, said oilsands is producing oil using standard extraction techniques. In oneembodiment, the method further comprises, prior to said introducing ofstep b), the step of discontinuing extraction of materials from said oilsands by said standard extraction techniques. In one embodiment, themethod further comprises, after said recovering of step c), the step ofrecirculating said oil sands. In one embodiment, the method furthercomprises, after said recirculating, the step of returning said oilsands to service and extracting oil by standard extraction techniques.In one embodiment, said formulation comprises approximately 30-35 oreven 30-45 weight percent of said one or more terpenoid compounds,approximately 30-35 or even 30-45 weight percent of said methyl esters,and the balance of weight percent of said glycol ether esters. In oneembodiment, said one or more terpenoid compounds comprise one or more ofpinene, menthene, menthane, and limonene. In one embodiment, one or moreterpenoid compounds comprises at least D-limonene. In one embodiment,further comprises after said recirculating step the steps of:introducing a second portion of said formulation into said oil sandsusing a first pressure, wherein said first pressure is greater thanambient atmospheric pressure; wherein said second pressure is greaterthan ambient atmospheric pressure; maintaining a third pressure in saidwell for 24 to 72 hours, wherein said third pressure is greater thanambient atmospheric pressure. In one embodiment, said first pressure isbetween about 200 psi and about 1000 psi, and wherein said secondpressure is between about 400 psi and about 1200 psi, and wherein saidthird pressure is between about 600 psi and about 1400 psi. In oneembodiment, the mixture is added to oil sands to enable the recovery ofotherwise uncapturable oil.

Definitions

To facilitate the understanding of this invention, a number of terms aredefined below. Terms defined herein have meanings as commonly understoodby a person of ordinary skill in the areas relevant to the presentinvention. Terms such as “a”, “an” and “the” are not intended to referto only a singular entity, but include the general class of which aspecific example may be used for illustration. The terminology herein isused to describe specific embodiments of the invention, but their usagedoes not delimit the invention, except as outlined in the claims.

Asphalt is a black bituminous material used for paving roads or otherareas; usually spread over crushed rock. Asphalt is also a darkbituminous substance found in natural beds and as residue from petroleumdistillation; comprised mainly of hydrocarbons. Asphalt is also a mixedasphalt and crushed gravel or sand; used especially for paving but alsofor roofing.

Asphalts, as used herein, include cementitious materials in which thepredominating constituents are bitumens that occur in nature or areobtained in petroleum processing. Bitumen is a term which encompassescementitious substances, natural or manufactured, composed principallyof high molecular weight hydrocarbons, of which asphalts, tars, pitches,and asphalitites are typical. Asphalts are often classified as solids,semisolids, or liquids. They are often defined as the manufacturedmaterials that are produced during petroleum processing. Asphaltscharacteristically contain very high molecular weight molecular polarspecies, called asphaltenes, which are soluble in carbon disulfide,pyridine, aromatic hydrocarbons, chlorinated hydrocarbons, andtetrahydrofuran (THF). Asphalts produced from the refining of petroleumhave been used primarily in paving and roofing applications.

In one embodiment, natural gas condensate or condensate is a low-densitymixture of hydrocarbon liquids that are present as gaseous components inthe raw natural gas produced from many natural gas fields. In oneembodiment, it condenses out of the raw gas if the temperature isreduced to below the hydrocarbon dew point temperature of the raw gas.In one embodiment, the natural gas condensate is also referred to assimply condensate, or gas condensate, or sometimes natural gasolinebecause it contains hydrocarbons within the gasoline boiling range. Rawnatural gas may come from any one of three types of gas wells: In oneembodiment, such as crude oil wells, raw natural gas that comes fromcrude oil wells is called associated gas. In one embodiment, this gascan exist separate from the crude oil in the underground formation, ordissolved in the crude oil. In one embodiment, such as dry gas wells,these wells typically produce only raw natural gas that does not containany hydrocarbon liquids. In one embodiment, such gas is callednon-associated gas. In one embodiment, such as condensate wells, thesewells produce raw natural gas along with natural gas liquid. In oneembodiment, Such gas is also non-associated gas and often referred to aswet gas.

A preferred rubber is at least a poly(conjugated diene). Exemplaryconjugated diene contributed monomer units include 1,3-butadiene,isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Preferredconjugated diene contributed monomer units are 1,3-butadiene andisoprene. The rubber may include more than one conjugated dienecontributed monomer unit, such as, for example, the rubber may be apoly(1,3-butadiene-co-isoprene).

In addition, the rubber may also contain additional monomer contributedunits. Exemplary monomer contributed units include vinyl-substitutedaromatic hydrocarbons. Suitable vinyl-substituted aromatic hydrocarbonsinclude styrene, α-methylstyrene, 1-vinylnaphthalene,2-vinylnaphthalene, 1-α-methyl vinylnaphthalene, 2-α-methylvinylnaphthalene, as well as alkyl, cycloalkyl, aryl, alkaryl, andaralkyl derivatives thereof, and di- or tri-vinyl aromatic hydrocarbons.A preferred vinyl-substituted aromatic hydrocarbon is styrene. Therubber is preferably any of poly(1,3-butadiene), styrene-butadienediblock polymers, as well as any styrene-butadiene block or randompolymers, and mixtures thereof.

Limonene is a colourless liquid hydrocarbon classified as a cyclicterpene possessing a strong smell of oranges. D-limonene has thestructure as shown below:

Limonene is a chiral molecule, and biological sources produce oneenantiomer: the principal industrial source, citrus fruit, containsD-limonene ((+)-limonene), which is the (R)-enantiomer. Racemic limoneneis known as dipentene [1]. D-Limonene is obtained commercially byextraction from orange peel with supercritical CO₂.

The term “effective,” as that term is used in the specification and/orclaims, means adequate to accomplish a desired, or hoped for result.

DESCRIPTION OF THE FIGURES

FIG. 1 shows a graphical representation of a well head 41 from the KernRiver Field demonstrating a significant decrease in the viscosity, andan increase in the oil produced with the formulation.

FIG. 2 shows a graphical representation of a well head 47 from the KernRiver Field demonstrating a significant decrease in the viscosity, andan increase in the oil produced with the formulation.

FIG. 3 shows a graphical representation of a well head 72 from the KernRiver Field demonstrating a significant decrease in the viscosity, andan increase in the oil produced with the formulation.

FIG. 4 shows an FTIR spectrum analysis of the Formula “A” also known asProdigen X.

FIG. 5 shows an FTIR spectrum analysis of the Formula “B”

FIG. 6 shows an FTIR spectrum analysis of the Formula “C”

FIG. 7 shows an FTIR spectrum analysis of of the AR 3600 asphaltremover.

Table 1 shows the viscosity of a crude oil sample with the addition ofcorresponding % of solution “A” from the present invention.

DESCRIPTION OF THE INVENTION

Crude oils of various composition and viscosities are hydrophobic andare difficult to remove due the high surface tension and the generalinsolubility with many inorganic and organic solvents. Detergent systemsdesigned to reduce the surface tension have met with limited success;however, the resulting mixtures are often surface contaminants, or maycause rusting or other forms of corrosion. Generally, the solvents usedto thin crude oil come form distillation fractions of crude oil, andcarry the same toxic compounds present in the crude oil. In addition,these agents can destroy the integrity of the crude oil and itssoluates, thus preventing the recovery and use of the materials removed.Further, these materials make it extremely difficult or impossible torecover the crude oil due to physical destruction of the crude.

There are several other needs for effective oil thinning agents. Theyare:

1. In Situ: There is a significant need for crude oil thinning in thegeologic formation containing the oil. Approximately 40-60% of theavailable crude in a well is left due to viscosity and surface tensionof the crude oil. The oil molecules “stick together” and on the surfacesof the formation, holding the oil back from flowing into the reservoirof the well. Oil wells are drilled into a geologic formation, whichcontains sufficient quantities of crude oil (or natural gas) to make iteconomically viable. Either a reservoir is present, or one isestablished to collect the crude oil so it can be pumped to the surface.Various technologies are used to “enhance” the oil to flow into thereservoir, including CO₂ injection under pressure, superheated steam,propane, detergents and acids, and forced air. Further, chemical andphysical “fracing” (also called fraccing or fracking) or fracturing theformation is a common practice to open the formation for more oil toflow into the collection reservoir. There are major issues with the usedetergents and acids because of the chemical alteration of the crudeoil, and additional pollution. Similar issues exist with the use ofsuperheated steam (water discharge), and the depletion of the watertable.

Opponents of fraccing point to the negative impact on the environmentand health, including contamination of ground water and the migration ofgases and hydraulic fracturing chemicals to the surface, as well assurface contamination from spills. Importantly, the plant-derivedformulations described herein can be an aid to fraccing, since they arenon-toxic, thereby reducing the potential for environmental damage.

2. Oil or tar sands oil recovery. Current technologies use highsuperheated steam to force the oil to be released from the ‘Mud” orsands. In most areas this is achieved by mining the oil mud, placing iton trucks, and carrying the mud to a processing site. No In Situprocessing is conducted. Similar problems are created using steam forthis use.

3. Crude oil transport via pipelines. Crude oil is transported from thewell head to the storage area, refinery, or ship via large, heatedpipes. Generally, the oil has been diluted with condensate (ahydrocarbon liquid/gas) present in all wells. The condensate gases areusually burned off and the liquid is used to thin the crude. The amountof condensate to crude oil may be anywhere from very liitte condensateto as much as 50%. In some instances, a 50% blend of synthetic oil isadded to reduce the viscosity and thus, the surface tension to allow oilto flow. Heat is always present in the transport pipes. Generally, theoil is heated to 90° C. to allow it to flow freely. This representsadditional energy consumption to allow oil to flow. A corrosioninhibitor is always added (1-2%) to reduce the chemical attack of thecrude on the pipeline walls.

This invention is described in preferred embodiments in the followingdescription with reference to the Figures, in which like numbersrepresent the same or similar elements. Reference throughout thisspecification to “one embodiment,” “an embodiment,” or similar languagemeans that a particular feature, structure, or characteristic describedin connection with the embodiment is included in at least one embodimentof the present invention. Thus, appearances of the phrases “in oneembodiment,” “in an embodiment,” and similar language throughout thisspecification may, but do not necessarily, all refer to the sameembodiment.

The described features, structures, or characteristics of the inventionmay be combined in any suitable manner in one or more embodiments. Inthe following description, numerous specific details are recited toprovide a thorough understanding of embodiments of the invention. Oneskilled in the relevant art will recognize, however, that the inventionmay be practiced without one or more of the specific details, or withother methods, components, materials, and so forth. In other instances,well-known structures, materials, or operations are not shown ordescribed in detail to avoid obscuring aspects of the invention.

As a result of the problems described, I was able to discover andperfect novel formulations which can be used to extract, retrieve andrecover the following: Thin crude oils, oil based tar sands, and allowthe recovery of crude oil from “oil rock” (oils impregnated or bound bysandstone or other naturally occurring aggregates with economicallyviable formulations that: a) require no heat, b) use no water, c) offerrecovery of the formulations up to, and inclusive of 94% of the originalamount used through physical or mechanical separation, d) convert topolyols if no recovery is required, e) are either the majority orcompletely biobased in content (non-toxic, thus non-polluting), f)combine readily with all types of crude oil, g) increase the well headyield of crude oil from 200-1,000%, h) free oil lodged in formationsallowing total recovery of available oil reserves in a well from 50-60%to 80% plus, i). Separate oil from water based emulsions and mixtures,allowing greater oil recovery

In one embodiment, the preferred chemistry comprises of anon-saponifiable cyclic monoterpene containing 2 isoprene units, withthe “d” configuration, specifically d-limonene reacted with soy methylesters and non-toxic glycol ether esters added in a specific sequence inthe presence of an inorganic catalyst. (Other monoterpines includingpinene, menthol, and turpentine, do not work, nor do additional isopreneunits making up the sesquiterpenes, diterpines, triterpenes, andtetraterpenes respectively. The “L” forms of all structures, including1-limonene do not react to form the end products.)

The reaction is a series of endothermic reactions resulting in a clear,water white to hazy yellow thin liquid. Each of the reactants can bevaried in concentration within limits in order to produce a slightlyaltered material formulated to achieve the specific functional result ofthinning crude oil per environmental application (Injection orgravimetric application into the formation, injection (In situ or underpressure in the formation or reservoir), continuing drip or singlecharge into the reservoir application, or combining with the crude oilpost well for transport, or spray or flooding on oil sands to releasethe bound oil.

The reaction steps are very specific. We tried other ways to react thematerials but the end product did not work very well.

Preferred Embodiments: Reaction Sequence

In one embodiment, 30-35% or even 30-45% (by weight) of d-limonene isplaced in a stainless steel reactor. An inorganic (e.g. iron/copper)catalyst is suspended in the solution. Note: the catalyst must extend tothe full length of the reactant results (it has got to be as long as thetank or vessel). In one embodiment, the reaction must be run in astainless or other steel tank in order to set up an electrolyticreaction between the dissimilar metals. We have repeatedly try toachieve the same results in glass and plastic containers with just thecopper catalyst, the results are solutions that don't work any wherenear as well on oil thinning. When we add a steel rod, strip, or othersource of steel to the glass or plastic vessel, we get great end productthat works well. A 30-35% addition of soy methyl esters (methyl soyatederived from soybean oil) is added and the resulting mixture is stirredat 1700-3500 rpm for 30 minutes. The reactor must be grounded.

The intermediate solution will gradually change color from a clear toslightly yellow color to a golden yellow, have a pH of between 4.0-5.0depending on the specific ratio of the two starting materials. A slighthaze will form in the solution.

Glycol ether esters are the added (to make up the balance) and thesolution is stirred (in the presence of the catalysts) for 1 hour oruntil the solution clears. In one embodiment, The temperature of thefinal solution will be at least 10 degrees lower than the surroundingambient conditions.

Physical and Chemical Properties: (at STP)

pH: 4.3-4.8Specific gravity: 0.8810-0.8900 (water=1.000)

Density: 7.09-7.10#/US Gallon

Surface tension: 10.5-11 dynes/cm²Odor: Aromatic, sweet fruity

Boiling Point: 185-190° F.

Flash Point: 140° F. (Tag Closed Cup), 70° F. (Penske, open cup)Solubility in water: Insoluble

Oil Thinning

A ratio of 30% d-limonene, 30% methyl soyates, 40% glycol ether estersapplied to heavy crude oil at STP, having a viscosity of 22,500 cTs.

Start viscosity of Crude Oil 22,500 (all applications done on aweight/weight basis, mixed for 2 minutes by hand) the viscosity resultsare shown in Table 1.

Crude oil cannot be efficiently pumped through pipelines unless theviscosity is reduced to a minimum high measurement of 350 cTs. This isthe international standard used for all pipeline transport of crude oil.The viscosity is lowered with the assistance of heat and the inclusionof condensates.

The attached study performed by (Enbridge) clearly describes theperformance of the solution, which includes the variable range of rawreactants. Formula “A” is the final formulation which uses theBituminous Substance Removal formulation as a primary building block ofthe cyclic monoterpene and the surfactant, The addition of the otherprimary raw materials previously identified in this document areessential for the viscosity and surface tension reduction to occur.

A study performed on a sample of crude oil obtained from Cushing,Oklahoma was evaluated using “formula A” for viscosity reduction,recovery of the solution, and surface tension. The results are asfollows:

Original viscosity 4,500 cTs surface tension: 31 dynes/cm² Add 3.5% “A”  375 cTs surface tension: 18 dynes/cm²

Thinning Agent-Distillation/Recovery

The following steps were used to recover up to 94% of the originalSolution. A simple. Low temperature distillation of the oil/solutionmixture was employed. Water was removed by one of two methods. The firstmethod was tested at a well site in OK.

The first method used a simple skimming operation whereby the crudeoil/our formula “A” mixture was separated from the water phase bygravimetric separation. The oil phase always floats above the waterphase. When this method was utilized, our material helped separate thephases significantly better than all other separation methods, andhelped remove suspended salts from the crude.

The second method was performed in a laboratory. This method used simplecentrifugation, whereby the crude oil/formulation “A” mixture wasseparated from the water phase. The problem with centrifugation is thatthere was some oil/“formulation “A” loss, and the residual fluid wasprocessed through a gravimetric separator to eliminate toxic materialdischarge back into the watershed.

Once the oil/formulations “A”, “B”, and “C” were separated from thewater phase, a low temperature, simple distillation/condensing recoverysystem was used to separate the crude oil from the oil phase. A meantemperature of less than 150° C. allowed intact recovery of almost allof the formulations. Recovery averages ranged from a low of 85%(Formulation “C”) to a High of 97%+(Formulation “A”). Mean recoverylevels of 94% were the target level, with solutions “A and B” wererecovered and tested for reuse in thinning fresh crude.

Experimental Field Results

The study of formulation “A”, referred to as AR-OT demonstrates theincreased flow of crude oil from the well following the introduction ofour material. The data, following a 1 month experimental trial, speaksfor itself with the increased output derived in situ.

Well head studies on wells #37, 41,47-72 from the Kern River Fielddemonstrate a significant decrease in the viscosity, and an increase inthe oil produced with the formulation (shown in FIG. 1, FIG. 2, and FIG.3).

The Glen Rose study and the Mega West data on “Prodigen X (which isFormulation “A”), clearly shows the significant improvements in flow andstem injection in the wells and in the formation with the use of ourmaterial.

FT-IR scans of Formulation “A,” “B,” and “C” (shown in FIG. 4, FIG. 5,and FIG. 6, respectively) attached and a scan of AR3600 (BituminousSubstance Removal product), shown in FIG. 7 is included for comparativeuse.

Samples of raw MacKay River Bitumen (MKB), and Coid Lake heavy crude oilwere provided by Enbridge for evaluation and testing. Condensate wasalso supplied since this is used as the primary diluent Synthetic oilwas not supplied

The primary objective with the MacKay River Bitumen were to reduce theviscosity of the MKB with a limited amound of BioSpan material,eliminating the need to heat the bitumen to 90° C. for transport to theblending facility where it is blended with a synthetic oil at a 50:50ratio, and to further reduce the amound of diluent to achieve a targetof 350 centistokes at a temperature of 11.9° C.

The second set of objectives were to reduce the Cold Lake blended crudeviscosity below 350 cSt with a small amound of the same BioSpan solutionused to reduce the viscosity of the MKB, if possible.

There were secondary objectives as follows:

-   -   1. Reduce, or eliminate the need for corrosion inhibitors added        to the crude oil flowing through the pipelines.    -   2. Be able to recover the BioSpan diluent solution at a minimal        80% level, with 85-90% recovery preferred.    -   3. Maintain the NON-TOXIC nature of the BioSpan solution(s).    -   4. Reduce the toxicity of the final diluent when condensate is        incorporated into the formulation    -   5. Availability of raw materials to meet demand.

Experimental Laboratory Methods:

All testing was conducted using currently accepted scientific methods.Hot and cold water bath were used to maintain constant temperatureduring testing. A Brookfield viscometer was used to measure viscosityand a distillation set u was used to replicate the initial recovery ofthe BioSpan Material at the refinery or other processing facility. GC/MSwas used to determine if there were any changes in the chemicalstructure, comparing the recovered crude or bitumen versus the undilutedmaterial, and the BioSpan solution(s). A Hewlett Packarad 5988A GC/MSwas used. Initial substrate compatibility was evaluated using blacksteel pipe following an accepted FDA protocol for corrosion resistance.

Over 60 different formulation modifications were evaluated for MKBviscosity reduction, staring at a temperature of 90° C., andsequentially reducing the temperature by 10° C. on those formulationsexpressing significant viscosity reduction as the temperature wasreduced. The concentration level of test solutions started at 10% andwas adjuste dupwar to reach the end point goals of the project It wasour goal to incorporate the condensate as part of the diluent, sincethis material is already been recovered and must be disposed of.

Condensate diluent was used at the 70% MKB: 30% condensate level as astandard.

Final testing and all other analysis were performed once the 11.9° C.viscosity level was achieved on the MKB samples. Recovery of the BioSpandiluent was done on these materials, as were the GC/MS tests.

Similar testing was performed on the Cold Lake material, but at a muchlwer level, since our target was to come up with a diluent reducer, orreplacement.

All testing was done on a weight/weight basis.

Results:

-   -   1. Three formulations demonstrated that the targeted viscosity        of 350 cSt or less is achievable at 11.9° C.    -   2. The amount of BioSpan material to achieve this goal ranges        from 11.45% to 18.0%.    -   3. Condensate may be combined with BioSpan materials at a ratio        of 50:50 or higher depending on the desired        viscosity/temperature ratio.    -   4. All formulations tested are completely hydrophobic.    -   5. All formulations are recoverable at a range of 85% or higher.

Formula “A”

Formula “A” is a non-toxic formulation that eliminates the need forcondensate. An 18% (by weight) use level of Formula “A” completelysolubilizes MKB at 19° C. resulting in a viscosity of 200-225 cSt, andat 11.9° C. the viscosity was 250-275 cSt. Solubilization speed is muchbetter than other formulations. Slightly increased temperatures ofbetween 30 and 40° C. result in almost immediate dissolution. At 60° C.,the dissolution is immediate, with little or no agitation needed.

Distillation recovery of this formulation is between 90 and 94% with noapparent change in the structure. The formulation is a corrosionprotectant, and a version of the base formulation is marked for this useon salt trucks and other heavy equipment exposed to chlorides andmoisture.

Serial reductions of this formulation at a ratio of 1 part “A” to 3parts condensate provides a similar viscosity reduction level with MKB;however, a linear increase in mixing temperature is necessary to easilycombine the diluent since the initial solubility of thecondensate/Formulat “A” is not as quick at 11.9° C. as a straightFormula “A.” Toxicity becomes an issue when condensate is combined withFormula “A” due to the inherent nature of the condensate.

An equal belend of Formula “A” and condensate at the 9% condentrationlevel of each came closest to using a 18% concentration of Formula “A.”

Formula “B”

Formula “B” is a modification of Formula “A.” The use level of thisformulation is approximately 15%, with a 15% addition of condensate. Itrapidly solubilizes the MKB at 50° C. The viscosity at 11.9° C. is 350cST, and has similar (but not quite as good as Formula “A”) corrosionprotection characteristics. The ratio of Formula “B” to condensate isroughly 1:4. The base solution is non-toxic, but will exhibit similartoxicity characteristics as “A” when combined with condensate.

One advantage is that it reduces the viscosity of the Cold Lake materialto ˜250 cSt with a 3-4% addition at 11.9° C. It mixes immediately into auniform liquid and is recoverable at a rate of approximately 85-90%. Nosignificant observable changes were seen on the GC/MS scans.

Formula “C”

Formula “C” has a different formula than “A or B.” It is non-toxic, buthas a higher boiling point that the other two formulations. At a useconcentration of 11.45%, the viscosity measured 350 cSt, at 19° C. Whenthe temperature was lowered to 11.9° C., the viscosity jumped to almost500 cSt. We attempted to reduce the viscosity by altering theformulation components without success; however this formulation didcombine with the Cold Lake samples reducing the viscosity to 300 cStwith a 5% addition to the Cold Lake product. Recovery throughdistillation was as the 80-85% level.

CONCLUSIONS

-   -   1. Of the 67 formulations evaluated under the criteria set forth        by Enbridge, three (3) formulations were identified as potential        candidates that met most, if not all the performance needs.    -   2. Formulat “A” met all the criteria set forth this far. It is        non-toxic, equipment friendly, environmentally friendly, and        does not alter the structural integrity of the crude oil while        liquefying the MKB, and reducing the viscosity of the Cold Lake        material. It is recoverable, and may be reusable if desired. It        combines readily with condensate, and the resulting mixture        offers a significant energy savings by reducing the need for        elevated temperature when liquefying the MKB. Sufficient raw        materials are available to keep us with demand, and provide        secondary benefits in maintaining the pipelines with reduced        corrosion.    -   3. Formula “B” provided similar results as Formula “A” but used        more materials and requires a higher mix temperature. It        combines readily with the Cold Lake crude, and sufficien raw        materials are available to meet future needs. It is recoverable        without significant changes to the integrity of the crude. It        mixes with condensate, but requires more condensate use than        Formula “A” to achieve similar results.    -   4. Formula “C” offers the lowerst use concentration, but        requires higher mix temperatures and does not provide the same        kind of corrosion protection as the other formulations. Of the        three, this formulation would require additional extensive        research on MKB in order to achieve the desired performance        characteristics.

REFERENCES

-   1. Simonsen, J. L. (1947) The Terpenes, Vol. 1, 2nd ed., Cambridge    University Press.

TABLE 1 Viscosity % Solution 22,500 0.00 19,500 1.00 17,600 1.50 15,9002.00 14,700 2.50 12,300 3.00 11,000 3.50 9,500 4.00 8,000 4.50 6,7705.00 5,100 5.50 4,000 6.00 2,950 6.50 1,800 7.00 950 7.50 951 8.00 9528.50 270 9.00

1-21. (canceled)
 22. A method to improve oil flow from an oil pipe,comprising: a) providing a formulation comprising: one or more terpenoidcompounds, soy methyl esters, and glycol ether esters; b) introducing afirst portion of said formulation into said oil pipe; and c) recoveringa mixture from said oil pipe, said mixture comprising at least a portionof said formulation and oil from said oil pipe.
 23. The method of claim22, wherein said pipes comprise oil field pipes.
 24. The method of claim22, wherein said formula is added to oil pipes in order to clear ablockage.
 25. The method of claim 24, wherein said blockage comprises aparaffin plug.
 26. The method of claim 24, wherein said mixturecomprises a paraffin plug treatment.
 27. The method of claim 22, whereinsaid pipes are buried pipes.
 28. The method of claim 22, wherein saidpipes are exposed to extreme temperatures.
 29. The method of claim 22,wherein said extreme temperatures comprises as low as −60° C.
 30. Themethod of claim 22, wherein said extreme temperatures comprises as lowas 40° C.
 31. The method of claim 22, wherein said formula is added tosaid oil pipe to enable the recovery of otherwise uncapturable oil. 32.The method of claim 22, wherein said one or more terpene comprisesD-limonene.
 33. The method of claim 22, wherein said formulationcomprises approximately 30-45 weight percent of said one or moreterpenoid compounds, and approximately 30-45 weight percent of saidmethyl esters.
 34. The method of claim 22, wherein said formulationcomprises about 20-30 weight percent of said glycol ether esters.